IEC 62321-6:2015

IEC 62321-6 ®
Edition 1.0 2015-06
INTERNATIONAL
STANDARD
NORME
INTERNATIONALE
colour
inside
HORIZONTAL STANDARD
NORME HORIZONTALE
Determination of certain substances in electrotechnical products –
Part 6: Polybrominated biphenyls and polybrominated diphenyl ethers in
polymers by gas chromatography–mass spectrometry (GC-MS)

Détermination de certaines substances dans les produits électrotechniques –
Partie 6: Diphényles polybromés et diphényléthers polybromés dans des
polymères par chromatographie en phase gazeuse–spectrométrie de masse
(GC-MS)
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IEC 62321-6 ®
Edition 1.0 2015-06
INTERNATIONAL
STANDARD
NORME
INTERNATIONALE
colour
inside
HORIZONTAL STANDARD
NORME HORIZONTALE
Determination of certain substances in electrotechnical products –

Part 6: Polybrominated biphenyls and polybrominated diphenyl ethers in

polymers by gas chromatography–mass spectrometry (GC-MS)

Détermination de certaines substances dans les produits électrotechniques –

Partie 6: Diphényles polybromés et diphényléthers polybromés dans des

polymères par chromatographie en phase gazeuse–spectrométrie de masse

(GC-MS)
INTERNATIONAL
ELECTROTECHNICAL
COMMISSION
COMMISSION
ELECTROTECHNIQUE
INTERNATIONALE
ICS 13.020; 43.040.10 ISBN 978-2-8322-2689-6

– 2 – IEC 62321-6:2015 © IEC 2015
CONTENTS
FOREWORD . 6
INTRODUCTION . 8
1 Scope . 9
2 Normative references. 9
3 Terms, definitions and abbreviations . 10
3.1 Terms and definitions . 10
3.2 Abbreviations . 10
4 Principle . 11
5 Reagents and materials . 11
6 Apparatus . 11
7 Sampling . 12
8 Procedure . 12
8.1 General instructions for the analysis . 12
8.2 Sample preparation . 12
8.2.1 Stock solution . 12
8.2.2 Pre-extraction of the Soxhlet extractors . 13
8.2.3 Extraction . 13
8.2.4 Alternative extraction procedures for soluble polymers . 13
8.2.5 Addition of the internal standard (IS) . 14
8.3 Instrumental parameters . 14
8.4 Calibrants . 16
8.5 Calibration . 17
8.5.1 General . 17
8.5.2 PBB (1 µg/ml for each congener), PBDE (1 µg/ml for each congener)
and surrogate standard (1 µg/ml) stock solution . 18
8.5.3 Standard solutions . 18
9 Calculation of PBB and PBDE concentration . 19
9.1 General . 19
9.2 Calculation . 19
10 Precision . 21
10.1 Threshold judgement . 21
10.2 Repeatability and reproducibility . 22
11 Quality assurance and control . 22
11.1 Resolution. 22
11.2 Performance . 23
11.3 Limit of detection (LOD) or method detection limit (MDL) and limit of
quantification (LOQ) . 24
12 Test report. 25
Annex A (informative) Determination of PBB and PBDE in polymers by ion attachment
mass spectrometry (IAMS) . 26
A.1 Principle . 26
A.2 Reagents and materials . 26
A.3 Apparatus . 26
A.4 Sampling. 27
A.4.1 General . 27
A.4.2 Qualitative stage . 27

A.4.3 Semi-quantitative stage . 27
A.5 Procedure . 27
A.5.1 General instructions for the analysis . 27
A.5.2 Sample preparation . 27
A.5.3 Instrumental parameters. 28
A.5.4 Calibrants . 29
A.5.5 Calibration . 29
A.6 Calculation of PBB and PBDE concentration . 30
A.6.1 General . 30
A.6.2 Calculation . 31
A.6.3 Judgement of ambiguous spectrum . 32
A.7 Precision . 34
A.7.1 Threshold judgement . 34
A.7.2 Repeatability and reproducibility . 34
A.8 Quality assurance and control . 35
A.8.1 Sensitivity . 35
A.8.2 Recovery . 35
A.8.3 Blank test . 36
A.8.4 Limits of detection (LOD) and limits of quantification (LOQ) . 36
A.9 Test report . 36
Annex B (informative) Diagram of an IAMS instrument . 37
Annex C (informative) Determination of PBB and PBDE in polymers by high-pressure
liquid chromatography – Ultra violet detection (HPLC-UV) . 38
C.1 Principle . 38
C.2 Reagents and materials . 38
C.3 Apparatus . 38
C.4 Sampling. 39
C.5 Procedure . 39
C.5.1 General instructions for the analysis . 39
C.5.2 Sample preparation . 39
C.5.3 Instrumental parameters. 40
C.5.4 Calibrants . 40
C.6 Calibration . 41
C.6.1 General . 41
C.6.2 Standard solutions . 41
C.7 Calculation of PBB and PBDE concentration . 42
C.7.1 General . 42
C.7.2 Calculation . 42
C.8 Precision . 43
C.8.1 Threshold judgement . 43
C.8.2 Repeatability and reproducibility . 43
C.9 Quality assurance and control . 44
C.9.1 Standards spike recovery . 44
C.9.2 Internal control samples and blanks . 44
C.9.3 Limits of detection (LOD) and limits of quantification (LOQ) . 45
C.10 Test report . 45
Annex D (informative) Examples of chromatograms at suggested conditions . 46
D.1 GC-MS method . 46
D.2 IAMS method . 48

– 4 – IEC 62321-6:2015 © IEC 2015
D.3 HPLC-UV method . 52
Annex E (informative) Example applicability of the IAMS, HPLC and GC-MS test
methods . 53
Annex F (informative) Results of international interlaboratory study 4B (IIS4B) . 54
Bibliography . 57

Figure A.1 – Mass spectra of Deca BB and TBBA obtained in scan mode and profile
mode . 33
Figure A.2 – Identification of Tetra-BDE and Penta-BDE by isotope pattern recognition . 33
Figure B.1 – Diagram of an IAMS instrument . 37
Figure D.1 – Total ion chromatogram of PBDE mixture, BDE-1 to BDE-206 (5 µg/ml),
BDE-209 (50 µg/ml) . 47
Figure D.2 – Total ion chromatogram of PBB mixture (3,5 µg/ml) . 47
Figure D.3 – Total ion chromatogram of PBB and PBDE mixtures (BDE-1 to BDE-206 5
µg/ml, BDE-209 50 µg/ml, PBBs 3,5 µg/ml) . 48
Figure D.4 – Mass spectrum of each PBDE congener by IAMS-1 (TriBDE to HexaBDE) . 49
Figure D.5 – Mass spectrum of each PBDE congener by IAMS-2 (HeptaBDE to
DecaBDE) . 49
Figure D.6 – Mass spectra of technical OctaBDE(a) as mixture . 50
Figure D.7 – Temperature-programmed chromatography of each PBDE congener in the
quantitative analysis of the reference material (ERM EC-590) . 51
Figure D.8 – Chromatogram and UV spectrum of DecaBDE . 52
Figure D.9 – Chromatogram and UV spectrum of decaBB . 52
Figure D.10 – Chromatogram and UV Spectrum of OctaBDE. 52
Figure D.11 – Chromatogram and UV spectrum of octaBB . 52
Figure E.1 – Flow chart, example applicability of the IAMS, HPLC and GC-MS test
methods . 53

Table 1 – Matrix spiking solution . 13
Table 2 – Reference masses for the quantification of PBBs . 15
Table 3 – Reference masses for the quantification of PBDEs . 16
Table 4 – Example list of commercially available calibration congeners considered
suitable for this analysis . 17
Table 5 – Calibration solutions of PBBs and PBDEs . 18
Table 6 – IIS4B threshold judgement . 21
Table 7 – IIS4B repeatability and reproducibility . 22
Table 8 – Example calculation . 23
Table A.1 – Measurement condition of IAMS . 28
Table A.2 – Example list of commercially available calibrant reference materials
considered suitable for this analysis . 29
Table A.3 – Example PBDE response factor standards (i.e. BDE-WD (Wellington),
solution/ mixture of polybrominated diphenyl ether congeners(PBDE)) . 29
Table A.4 – Calibrant amounts . 30
a
Table A.5 – Response factor of each PBDE congener . 32
Table A.6 – IIS4B threshold judgement . 34
Table A.7 – IIS4B repeatability and reproducibility . 35

Table C.1 – Example list of commercially available technical calibration mixtures
considered suitable for this analysis . 41
Table C.2 – Standard stock solution concentrations (mg/100 ml) . 41
Table C.3 – IIS4B threshold judgement . 43
Table C.4 – IIS4B Repeatability and reproducibility . 44
Table D.1 – PBB and PBDE congeners in the mixture . 46
Table F.1 – Statistical Data for GC-MS . 54
Table F.2 – Statistical data for IAMS . 55
Table F.3 – Statistical data for HPLC-UV . 56

– 6 – IEC 62321-6:2015 © IEC 2015
INTERNATIONAL ELECTROTECHNICAL COMMISSION
____________
DETERMINATION OF CERTAIN SUBSTANCES
IN ELECTROTECHNICAL PRODUCTS –

Part 6: Polybrominated biphenyls and polybrominated diphenyl ethers
in polymers by gas chromatography–mass spectrometry (GC-MS)

FOREWORD
1) The International Electrotechnical Commission (IEC) is a worldwide organization for standardization comprising
all national electrotechnical committees (IEC National Committees). The object of IEC is to promote
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8) Attention is drawn to the Normative references cited in this publication. Use of the referenced publications is
indispensable for the correct application of this publication.
9) Attention is drawn to the possibility that some of the elements of this IEC Publication may be the subject of
patent rights. IEC shall not be held responsible for identifying any or all such patent rights.
International Standard IEC 62321-6 has been prepared by IEC technical committee 111:
Environmental standardization for electrical and electronic products and systems.
It has the status of a horizontal standard in accordance with IEC Guide 108.
The first edition of IEC 62321:2008 was a 'stand-alone' standard that included an introduction,
an overview of test methods, a mechanical sample preparation as well as various test method
clauses.
This first edition of IEC 62321-6 is a partial replacement of IEC 62321:2008, forming a
structural revision and generally replacing Annex A.
Future parts in the IEC 62321 series will gradually replace the corresponding clauses in
IEC 62321:2008. Until such time as all parts are published, however, IEC 62321:2008 remains
valid for those clauses not yet re-published as a separate part.

The text of this standard is based on the following documents:
FDIS Report on voting
111/368/FDIS 111/379/RVD
Full information on the voting for the approval of this standard can be found in the report on
voting indicated in the above table.
This publication has been drafted in accordance with the ISO/IEC Directives, Part 2.
A list of all parts in the IEC 62321 series, published under the general title: Determination of
certain substances in electrotechnical products, can be found on the IEC website
The committee has decided that the contents of this publication will remain unchanged until
the stability date indicated on the IEC web site under "http://webstore.iec.ch" in the data
related to the specific publication. At this date, the publication will be
• reconfirmed,
• withdrawn,
• replaced by a revised edition, or
• amended.
IMPORTANT – The 'colour inside' logo on the cover page of this publication indicates
that it contains colours which are considered to be useful for the correct
understanding of its contents. Users should therefore print this document using a
colour printer.
– 8 – IEC 62321-6:2015 © IEC 2015
INTRODUCTION
The widespread use of electrotechnical products has drawn increased attention to their impact
on the environment. In many countries this has resulted in the adoption of regulations
affecting wastes, substances and energy use of electrotechnical products.
The use of certain substances (e.g. lead (Pb), cadmium (Cd) and polybrominated diphenyl
ethers (PBDE’s)) in electrotechnical products is a source of concern in current and proposed
regional legislation.
The purpose of the IEC 62321 series is therefore to provide test methods that will allow the
electrotechnical industry to determine the levels of certain substances of concern in
electrotechnical products on a consistent global basis.
WARNING – Persons using this International Standard should be familiar with normal
laboratory practice. This standard does not purport to address all of the safety
problems, if any, associated with its use. It is the responsibility of the user to establish
appropriate safety and health practices and to ensure compliance with any national
regulatory conditions.
DETERMINATION OF CERTAIN SUBSTANCES
IN ELECTROTECHNICAL PRODUCTS –

Part 6: Polybrominated biphenyls and polybrominated diphenyl ethers
in polymers by gas chromatography–mass spectrometry (GC-MS)

1 Scope
This Part of IEC 62321 specifies one normative and two informative techniques for the
determination of polybrominated biphenyls (PBB) and diphenyl ethers (PBDE) in polymers of
electrotechnical products.
The gas chromatography–mass spectrometry (GC-MS) test method is suitable for the
determination of monobrominated to decabrominated biphenyls (PBB) and monobrominated to
decabrominated diphenyl ethers (PBDE).
Annexes A and C contain methods using ion attachment mass spectrometry (IAMS) coupled
with direct injection probe (DIP) and high-pressure liquid chromatography coupled to photo
diode array ultra violet detector (HPLC-PDA/UV). These techniques have utility as fast,
qualitative or semi-quantitative type methods but are subject to limitations including
interferences or the number or type of PBB and PBDE compounds within their scope.
The ion attachment mass spectrometry (IAMS) technique is limited to the determination of
decabromo biphenyl and technical mixtures of decabromodiphenyl ether, octabromodiphenyl
ether, and pentabromo diphenyl ether flame retardant compounds. The determination of other
PBBs or PBDEs by this method has not been evaluated.
The high-pressure liquid chromatography technique is limited to the determination of technical
mixtures of decabromodiphenyl ether, octabromo diphenyl ether, decabromo biphenyl and
octabromo biphenyl technical flame retardants. The determination of other PBBs or PBDEs by
this method has not been evaluated.
These test methods have been evaluated for use with PS-HI (polystyrene, high-impact) and
PC/ABS (a blend of polycarbonate and acrylonitrile butadiene styrene) containing individual
PBDEs between 20 mg/kg to 2 000 mg/kg and total PBDEs between 1 300 mg/kg to 5 000
mg/kg as depicted in this standard including in Annex F. The use of these methods for other
polymer types, PBBs or other PBDE compounds or concentration ranges other than those
specified above has not been specifically evaluated.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and
are indispensable for its application. For dated references, only the edition cited applies. For
undated references, the latest edition of the referenced document (including any
amendments) applies.
IEC 62321:2008, Electrotechnical products – Determination of levels of six regulated
substances (lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls,
polybrominated diphenyl ethers)
IEC 62321-1:2013, Determination of certain substances in electrotechnical products – Part 1:
Introduction and overview
– 10 – IEC 62321-6:2015 © IEC 2015
IEC 62321-2:2013, Determination of certain substances in electrotechnical products – Part 2:
Disassembly, disjointment and mechanical sample preparation
3 Terms, definitions and abbreviations
3.1 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1.1
semi-quantitative
level of accuracy in a measurement amount where the relative uncertainty of the result is
typically 30 % or better at a defined level of confidence of 68 %
3.1.2
technical mixture
commercial product (e.g. flame retardants) manufactured for industrial use whose purity is not
as clearly defined as an individual high purity calibration standard
3.2 Abbreviations
BDE brominated diphenyl ether
BFR brominated flame retardant
Br bromine
CIC combustion – ion chromatography
DIP direct injection probe
GC-MS gas chromatography-mass spectrometry
HPLC-UV high-performance liquid chromatography-ultra violet
IAMS ion attachment mass spectrometry
IS internal standard
MDL method detection limit
LOD limit of detection
LOQ limit of quantification
PBB polybrominated biphenyl
PBDE polybrominated diphenyl ether
PDA photodiode array (UV) detector
PS-HI (or HIPS) high impact polystyrene
PTV programmed temperature vaporising
QC quality control
SIM single (or “selected”) ion monitoring
XRF X-ray fluorescence spectroscopy
TICS tentatively identified compounds
RSD relative standard deviation
CCC continuing calibration check standard
BSA bis(trimethylsilyl)acetamide
BSTFA N,O-Bis(trimethylsilyl)trifluoroacetamide
BCR 681 Bureau Communautaire de Référence
NOTE BCR 681 contains 7 trace elements in a polyethylene matrix.
The certified value for Br is 98 mg/kg ± 5 mg/kg

GC gas chromatography
ABS acrylonitrile-butadiene-styrene plastic
PDA/UV photo diode array ultra violet detector
OFP octafluoro pentanol
PTFE polytetrafluoroethylene
4 Principle
PBB and PBDE compounds are quantitatively determined using Soxhlet extraction of the
polymers with separation by gas chromatography – mass spectrometry (GC-MS) qualitatively
and quantitatively using single (or “selected”) ion monitoring (SIM).
5 Reagents and materials
All reagent chemicals shall be tested for contamination and blank values prior to application
as follows:
a) toluene (GC grade or higher);
b) helium (purity of greater than a volume fraction of 99,999 %);
c) technical BDE-209 with BDE-209 ~ 96,9 % and BDE-206 ~ 1,5 % solution;
d) calibrants: refer to 8.4;
e) surrogate and internal standards
– surrogate standard used to monitor analyte recovery according to 8.2.1 a), 8.2.3 c),
8.2.4 e), 8.5.2 and 8.5.3, e.g. DBOFB (4, 4’-dibromooctafluorobiphenyl) (n),
– internal standard used to correct for injection errors, according to 8.2.1 b), 8.2.5 and
8.5.3, e.g. CB209 (2,2’,3,3’,4,4’,5,5’,6,6’-decachlorobiphenyl).
The standards are acceptable when using a quadrupole-type mass spectrometer. A high-
resolution mass spectrometer will require the use of other suitable standard substances
13 13
having a mass and elution time similar to that of the analyte. C-labelled nonaBDE and C-
labelled decaBDE are recommended for the high-mass PBDEs.
NOTE The standards suggested are adequate for measuring the concentrations of mono- through octaBDE. Due
to their low mass and “high” volatility, these standards can be inadequate for measuring decaBDE and nonaBDE
concentrations. By far the best calibration standard for these specific analytes would be C-labelled decaBDE or
one of the C-labelled nonaBDEs. Some laboratories, operating on the principal of high volume/low price, can find
these labelled materials too expensive for their business plan. A potential low-cost substitute is decaBB (BB 209).
BB 209 has a high mass (943,1 g/mol versus 959,1g/mol for decaBDE or 864,2 g/mol for nonaBDE), which elutes
just before the three nonaBDEs on a typical DB-5 column. The presence of significant quantities of decaBB in the
sample itself can readily be determined by monitoring the peak area of this standard, and comparing it to what is
expected from the added quantity of decaBB. The use of the suggested labelled standards or decaBB can be
limited to those analyses where the only analytes of interest are decaBDE and/or the nonaBDEs. With additional
experimentation it can be possible to identify alternate standards that have the high mass and low volatility
necessary for the quantification of the nonaBDEs and decaBDE.
6 Apparatus
The following items shall be used for the analysis:
a) analytical balance capable of measuring accurately to 0,000 1 g;
b) 1 ml, 5 ml, 10 ml, 100 ml volumetric flasks;
c) Soxhlet extractors
– 30 ml Soxhlet extractors,
– 100 ml round-bottomed flask,
– ground-in stopper NS 29/32,
– 12 – IEC 62321-6:2015 © IEC 2015
– Dimroth condenser NS 29/32,
– boiling stones (e.g. glass pearls or Raschig rings);
d) extraction thimble (cellulose, 30 ml, ID 22 mm, height 80 mm);
e) glass wool (for extraction thimble);
f) deactivated injector liner (for GC-MS);
g) heating jackets;
h) funnel;
i) aluminium foil;
NOTE Brown or amber vessels as indicated in the text of the procedure can also be used.
j) Microlitre syringe or automatic pipettes;
k) Pasteur pipette;
l) 1,5 ml sample vials with 100 µl glass insert and a screw cap with polytetrafluoroethylene
(PTFE) gasket or, depending on the analytical system, a comparable sample receptacle.
Brown or amber vessels shall used as indicated in the text of the procedure.
m) mini-shaker (also known as vortexer or vortex mixer);
n) a gas chromatograph with a capillary column coupled to a mass spectrometric detector
(electron ionization, EI) is used for the analysis. The mass spectrometric detector shall be
able to perform selective ion monitoring and have an upper mass range of at least
1 000 m/z. The high-range mass is required to unambiguously identify decaBDE and
nonaBDE. The use of an autosampler is strongly recommended to ensure repeatability;
o) a column length of approximately 15 m has sufficient separation efficiency for PBB and
PBDE compounds (see 8.3 a) for example of suitable column);
p) 0,45 µm PTFE filter membrane.
7 Sampling
As described in IEC 62321-2 unless indicated otherwise (e.g. “.using a nipper.”), cryogenic
grinding with liquid nitrogen cooling is recommended. The samples shall be ground to pass
through a 500 µm sieve before extraction.
8 Procedure
8.1 General instructions for the analysis
The following general instructions shall be followed:
a) In order to reduce blank values, ensure the cleanliness of all glass equipment (excluding
volumetric flasks) and deactivate glass wool (see Clause 6 e)) by subjecting it to 450 °C
for at least 30 min. To avoid decomposition and/or debromination of PBDEs by UV light
during extraction and analysis, glass equipment made from brown or amber glass shall be
used.
NOTE If no brown or amber glass is available, aluminium foil can be used for protection from light.
b) If the amount of Br in the sample (determined by XRF, CIC or other means) is
considerably above the 0,1 % range, it will be necessary to carry out the analysis using an
adjusted sample size or by repeating the analysis using an extract that has been
appropriately diluted prior to internal standard addition.
8.2 Sample preparation
8.2.1 Stock solution
The following stock solutions shall be prepared:

a) surrogate standard (to monitor analyte recovery): 50 µg/ml in toluene (e.g. DBOFB);
b) internal standard (to correct for injection error): 10 µg/ml in toluene (e.g. CB209);
c) polybrominated biphenyl (PBB) solution: 50 µg/ml in an organic solvent;
d) polybrominated diphenyl ether (PBDE) solution: 50 µg/ml in an organic solvent; all
brominated species from mono- to decabrominated biphenyl (PBB) and mono- to
decabrominated diphenyl ether (PBDE) shall be included in the PBB and PBDE stock
solutions (see 8.4). Other stock solution concentrations can be utilized providing the
standard solution concentrations given in 8.5.3 can be achieved.
e) matrix spiking solution; containing a total of four calibration congener standards in toluene
as indicated in Table 1. The addition of 1 ml of a matrix spiking solution containing each of
the four congeners in a concentration of 10 µg/ml is suitable for delivery of the required
10 µg (see 11.2 b)) in the matrix spike sample.
Table 1 – Matrix spiking solution
Level of bromination Number of PBDE congeners Number of PBB congeners
Mono to penta 1 1
Hexa- to deca- 1 1
8.2.2 Pre-extraction of the Soxhlet extractors
To clean the Soxhlet extractors (see Clause 6 c)), a 2 h pre-extraction is carried out with
70 ml of toluene. The washing solvent is discarded.
8.2.3 Extraction
The following steps shall be followed for sample extraction:
a) Quantitatively transfer 100 mg ± 10 mg of the sample into the extraction thimble (see
Clause 6 d)) through a funnel (see Clause 6 h)). In order to ensure a quantitative transfer,
the funnel is rinsed with approximately 10 ml of toluene extraction solvent. Record the
sample mass to the nearest 0,1 mg.
b) 200 µl of the surrogate standard (see 8.2.1 a)) (50 µg/ml) is added (in accordance with
8.2.1).
c) In order to prevent the sample from floating, the extraction thimble is closed with glass
wool (see Clause 6 e)). Approximately 60 ml of solvent is placed in the 100 ml round-
bottomed flask, the equipment is covered with aluminium foil to exclude light and the
sample is extracted for at least 2 h with each cycle being approximately 2 min to 3 min.
Shorter extraction times may result in lower recoveries of the analytes, particularly for the
higher molecular mass PBDEs.
d) The extract is placed in a 100 ml volumetric flask and the round-bottomed flask is rinsed
with approximately 5 ml of solvent.
NOTE If the solution exhibits turbidity due to the matrix, this can be reduced by adding 1 ml of methanol. The
difference between the density of methanol and toluene can be disregarded in t
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